CN112358581A - Functional assistant for liquid silicone rubber and preparation method and application thereof - Google Patents
Functional assistant for liquid silicone rubber and preparation method and application thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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Abstract
The invention discloses a functional assistant for liquid silicone rubber, which is mainly polymerized by acrylate monomers, vinyl siloxane and other vinyl monomer compounds according to the mass ratio of 80-300: 100-. The functional assistant successfully realizes the purpose of simultaneously carrying out several modifications on the liquid silicone rubber, thereby further improving the performance of the organosilicon material. The invention also discloses a preparation method of the functional assistant, which comprises the steps of mixing vinyl siloxane, acrylate monomers, a chain transfer agent and a solvent, then dropwise adding a chain initiator, other vinyl monomer compounds and the solvent, controlling the temperature to be 40-120 ℃, reacting for 2-8h to obtain a primary sample, then extracting, distilling under reduced pressure, and removing the solvent to obtain the functional assistant. The method is simple to operate, can smoothly realize industrial application, and is easy to effectively control the molecular structure, the polymerization degree and the like of the functional auxiliary agent.
Description
Technical Field
The invention belongs to the technical field of liquid silicone rubber, and particularly relates to a functional auxiliary agent for liquid silicone rubber, and a preparation method and application thereof.
Background
The liquid silicon rubber is a base material with self-leveling property or thixotropy prepared by using linear polyorganosiloxane with medium polymerization degree as a base polymer and matching with a filler, various auxiliary agents and additives, can be extruded, injected and coated according to varieties and purposes when in use, and then is vulcanized and formed into an elastomer in the atmosphere or under heating, and the main chain Si-O bond of the liquid silicon rubber has larger bond energy, so that the liquid silicon rubber endows the material with excellent flexibility, good temperature resistance, weather resistance and ageing resistance, and is widely applied to various fields of medical treatment, buildings, power electronics, rail transit industries and the like, such as moistureproof and insulating coating and encapsulating materials of electronic components, and plays roles of dust prevention, moisture prevention, shock prevention, insulating protection and the like on the electronic components and assemblies.
The liquid silicone rubber shows more excellent performances due to the special molecular structure, but still has more problems in practical use, and the application of the liquid silicone rubber is greatly limited. The liquid silicone rubber has relatively many researches on the improvement of the performance, such as adhesion, heat resistance, cold resistance, weather resistance, insulativity, oil resistance, chemical solvent resistance, radiation resistance, air permeability, thermal conductivity, flame retardance and the like, and the basic principle of the improvement is to introduce corresponding functional groups, such as fluorine-containing groups to obviously improve oil resistance and solvent resistance, phenyl groups to improve the heat resistance and cold resistance of the silicone rubber, and epoxy groups, hydroxyl groups and the like to improve the adhesion of the silicone rubber. The improved method mainly comprises the steps of introducing functional groups into basic compounds or cross-linking agent molecules and then carrying out formula design, but the method has more problems, namely, the general principle and process for introducing the functional groups into the basic compounds or the cross-linking agent molecules are complex, the yield is low, the purification is complicated, and most of the methods have obvious environmental protection problems, so that the industrial popularization is greatly limited; secondly, the modification process is basically single-function modification, and only one property or one class of properties of the silicon rubber can be improved in a single way. Therefore, most of the liquid silicone rubbers in the current market have the defects that the conventional liquid silicone rubbers have low cost, more applications but relatively poor performance, and the silicone rubbers with relatively good performance have high cost and are only used in the special application field, so that the use of the liquid silicone rubbers is greatly limited comprehensively.
Therefore, the development of a functional assistant which has low cost and excellent performance and can be used for liquid silicone rubber has very important significance for the technical field.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background art, and provide a functional auxiliary agent for liquid silicone rubber with low cost and excellent performance, and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a functional assistant for liquid silicone rubber is prepared from acrylate monomer, vinyl siloxane and other vinyl monomer compounds through polymerizing at a mass ratio of 80-150: 100-200: 20-120.
Preferably, the acrylate monomer is one or a combination of acrylic acid, methyl acrylate, butyl acrylate, hydroxyethyl methacrylate and perfluoroalkyl ethyl acrylate.
Preferably, the vinyl siloxane is a vinyl silicone oil. The vinyl siloxane is added to adjust the compatibility of the functional assistant and the liquid silicone rubber.
Preferably, the other vinyl monomer compound is one or a combination of several selected from styrene, vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, acrylonitrile and vinyl acetate. The function of adding other vinyl monomer compounds is to enrich the functional groups of the acrylate monomers and further improve the modification effect of the functional auxiliary agent on the liquid silicone rubber.
Preferably, the solubility parameter of the functional assistant is 10-25, the polymerization degree is 1-100, and the molecular weight is 1000-10000.
The functional assistant of the invention has three key points in synthesis: firstly, the functional auxiliary agent must have proper solubility parameter, polymerization degree and molecular weight, so that the functional auxiliary agent has better compatibility with an organosilicon system of liquid silicone rubber, and the functional auxiliary agent is a necessary characteristic for serving as an addition auxiliary agent or a further modifier; secondly, the functional assistant must have a suitable reactive group to enable the functional assistant to participate in the reaction of the liquid silicone rubber, such as hydroxyl, vinyl, a hydrogen-containing group, and the like; thirdly, the functional assistant must have one or more modified groups, so as to improve the comprehensive performance of the liquid silicone rubber, such as cyano, fluorine-containing groups, ester groups and the like.
Based on a general inventive concept, the present invention also provides a preparation method of the functional aid for liquid silicone rubber, comprising the following steps: mixing vinyl siloxane, acrylate monomers, a chain transfer agent and a solvent, then dropwise adding a chain initiator, other vinyl monomer compounds and the solvent, controlling the temperature to be 40-120 ℃, reacting for 2-8 hours to obtain a primary sample, then extracting, distilling under reduced pressure, removing the solvent, and finally obtaining light yellow viscous liquid, namely the functional assistant for the liquid silicone rubber.
The method is free radical solution polymerization, the reaction time and temperature are controlled by a chain initiator and a solvent, the termination of the reaction is controlled by a chain transfer agent, so that the polymerization degree and the molecular weight of a functional auxiliary agent are controlled, and the proportion of different functional groups of a polymer is controlled by the reactivity ratio and the addition amount of different monomers.
In the above preparation method, preferably, the solvent is one or a combination of several selected from toluene, xylene, acetone, butanone, ethyl acetate, heptane and cyclohexane.
Preferably, the chain initiator is selected from one or a combination of more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, potassium persulfate and ammonium persulfate, and the addition amount of the chain initiator is 0.1-10% of the total mass of all raw materials.
Preferably, the chain transfer agent is selected from one or a combination of more of isooctyl 3-mercaptopropionate, n-dodecyl mercaptan, quaternary cyclopentadienyl tetraethol tetrakis (3-mercaptopropionate) and ethyl hexyl 3-mercaptopropionate, and the addition amount of the chain transfer agent is 0.01-10% of the total mass of all raw materials.
Based on a general inventive concept, the invention also provides an application of the functional aid for the liquid silicone rubber, and particularly the functional aid is mixed with the liquid silicone rubber for use.
The main innovation of the invention has three key parts: firstly, in the molecular design of the functional auxiliary agent, different types of functional groups are selected to modify the liquid silicone rubber, and proper siloxane molecules are selected to perform compatibility modification, so that the functionality and the applicability of the functional auxiliary agent achieve the optimal effect; secondly, the monomers selected by the invention need to consider the requirements of molecular design to ensure that the functional auxiliary agent has corresponding functional groups, and comprehensively screen from the aspects of reactivity ratio and the like to select different types of molecular monomers with highest controllability and best feasibility, and quantitatively control the addition amount and the addition speed of each monomer according to the reactivity ratio condition, thereby strictly controlling the molecular structure, the polymerization degree and the molecular weight of the functional auxiliary agent; thirdly, the invention considers the final industrial application situation, selects a free radical solution polymerization method, considers the complexity of the monomers, specially selects and controls the solvent aiming at the problem of poor compatibility of different monomers, specially controls the monomer adding sequence and adding speed aiming at the problem of large reactivity ratio difference between the monomers, and carries out special control and treatment on the chain initiator and the chain transfer agent because the polymerization degree and the molecular weight have very critical influence on the performance of the functional assistant, thereby finally obtaining the controllable polymerization process which can be industrially applied.
Compared with the prior art, the invention has the advantages that:
(1) the functional assistant prepared by the invention has obvious reactive groups, such as hydroxyl, vinyl and the like, and the reactive groups can react with other siloxane to achieve the purpose of modification and have good modification effect;
(2) the solubility parameter of the functional additive prepared by the invention is similar to that of liquid silicone rubber, and tests prove that the functional additive has better compatibility with an organic silicon system of the liquid silicone rubber, thereby being beneficial to the application of the functional additive;
(3) the functional additive prepared by the invention has more active groups, the active groups can obviously improve the performance of liquid silicone rubber, for example, nitrile groups can obviously improve the adhesion and stain resistance of an organic silicon system, and fluorine-containing groups can obviously improve the oil resistance of the organic silicon system;
(4) the functional additive prepared by the invention selects a free radical solution polymerization method in the polymerization method, on one hand, the operation is simple, the industrial application can be smoothly realized, and on the other hand, the molecular structure, the polymerization degree and the like of the functional additive are effectively controlled by controlling a solvent, a chain initiator and a chain transfer agent;
in conclusion, the functional additive prepared by the invention is a feasible additive type additive or modification additive in industrial application, and successfully realizes the purpose of simultaneously carrying out several modifications on liquid silicon rubber, so that the performance of the organosilicon material is further improved, which is incomparable with other inventions.
Detailed Description
In order to facilitate an understanding of the invention, the invention will now be described more fully and in detail with reference to the accompanying description and preferred embodiments, but the scope of the invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a functional assistant for liquid silicone rubber is mainly prepared from acrylate monomers, vinyl siloxane and other vinyl monomer compounds by a proper polymerization method, and the specific preparation method is as follows:
(1) 200g of vinyl silicone oil (vinyl siloxane, the viscosity is 500mpa.s, the vinyl mass content is 0.43 percent), 0.2g of n-dodecyl mercaptan (chain transfer agent), 20.8g of perfluoroalkyl ethyl acrylate (acrylate monomer), 116g of hydroxyethyl acrylate (acrylate monomer) and 100g of acetone (solvent) are placed in a four-neck flask, the mixture is uniformly mixed, the temperature is increased to 80 ℃, a mixed solution is dripped while stirring, the mixed solution is formed by uniformly mixing 10g of AIBN (azodiisobutyronitrile, chain initiator), 80g of acetone (solvent) and 106g of acrylonitrile (other vinyl monomer compounds), the dripping rate is controlled, the dripping is kept at 80 ℃ within 90min, the reaction is carried out for 6h, a preliminary sample is obtained, then butanone-acetone mixed solution (the volume ratio of butanone to acetone is 1: 3) is selected for extraction, and reduced pressure distillation is carried out, and removing the solvent to obtain a light yellow viscous liquid, namely the functional assistant for the liquid silicone rubber.
The performance of the functional additives prepared in this example was tested and the results are shown in Table 1.
The functional additive prepared in this example was added to liquid silicone rubber (silicone three-proofing coating gum, a condensed silicone coating product), wherein the mass percentage of the functional additive was 2%, and performance tests and comparisons were performed, and the results are shown in table 2.
The solubility parameter of the functional auxiliary agent is 19.45, and the molecular weight is 9800.
Example 2:
a functional assistant for liquid silicone rubber is mainly prepared from acrylate monomers, vinyl siloxane and other vinyl monomer compounds by a proper polymerization method, and the specific preparation method is as follows:
(1) putting 200g of vinyl silicone oil (vinyl siloxane, the viscosity is 200mpa.s, the vinyl mass content is 0.70%) and 0.2g of isooctyl 3-mercaptopropionate (chain transfer agent), 20.8g of perfluoroalkylethyl acrylate (acrylate monomer), 65g of hydroxyethyl methacrylate (acrylate monomer) and 100g of acetone (solvent) into a four-neck flask, uniformly mixing, heating to 80 ℃, dropwise adding a mixed solution while stirring, wherein the mixed solution is prepared by uniformly mixing 8g of AIBN (azobisisobutyronitrile, chain initiator), 80g of acetone (solvent) and 53g of acrylonitrile (other vinyl monomer compounds), controlling the dropwise adding rate, keeping the temperature at 80 ℃ after the dropwise adding is finished within 90min, reacting for 8h to obtain a primary sample, and extracting by selecting a butanone-acetone mixed solution (the volume ratio of butanone to acetone is 1: 3), and then carrying out reduced pressure distillation, and removing the solvent to obtain light yellow viscous liquid, namely the functional assistant for the liquid silicone rubber.
The performance of the functional additives prepared in this example was tested and the results are shown in Table 1.
The functional additives prepared in this example were added to liquid silicone rubber (silicone three-proofing coating adhesive) for performance testing and comparison, and the results are shown in table 2.
The solubility parameter of the functional auxiliary agent is 20.21, and the molecular weight is 8700.
Example 3:
a functional assistant for liquid silicone rubber is mainly prepared from acrylate monomers, vinyl siloxane and other vinyl monomer compounds by a proper polymerization method, and the specific preparation method is as follows:
(1) putting 200g of vinyl silicone oil (vinyl siloxane, the viscosity is 200mpa.s, the vinyl mass content is 0.70%) and 0.2g of tetra (3-mercaptopropionic acid) metallocene tetraenol ester (chain transfer agent), 130g of hydroxyethyl methacrylate (acrylate monomer), 72g of acrylic acid (acrylate monomer) and 100g of acetone (solvent) into a four-mouth flask, uniformly mixing, heating to 80 ℃, dripping a mixed solution while stirring, wherein the mixed solution is prepared by uniformly mixing 8g of AIBN (azobisisobutyronitrile, chain initiator), 80g of acetone (solvent) and 106g of acrylonitrile (other vinyl monomer compounds), controlling the dripping rate, keeping the temperature at 80 ℃ after finishing dripping within 90min, reacting for 8 hours to obtain a primary sample, and extracting by selecting a butanone-acetone mixed solution (the volume ratio of butanone to acetone is 1: 3), and then carrying out reduced pressure distillation, and removing the solvent to obtain light yellow viscous liquid, namely the functional assistant for the liquid silicone rubber.
The solubility parameter of the functional auxiliary agent is 18.54, and the molecular weight is 7800.
The performance of the functional additives prepared in this example was tested and the results are shown in Table 1.
The functional assistant prepared in this example was added to liquid silicone rubber (silicone three-proofing coating adhesive), and 2% of the components of the liquid silicone rubber were added in proportion for performance testing and comparison, and the results are shown in table 2.
Table 1 basic performance test results of functional additives prepared in each example
| Item | Example 1 | Example 2 | Example 3 |
| Product traits | Light yellow liquid | Light yellow liquid | Light yellow liquid |
| Viscosity (mPa.s) | 4200 | 3600 | 2200 |
| Yield of | 75％ | 83％ | 81％ |
| Hydroxyl group content mmol/g | 1.02 | 0.98 | 1.13 |
| Compatibility with hydroxy silicone oils | Is preferably used | Is preferably used | Is preferably used |
Table 2 results of testing the effect of functional additives prepared in each example on the performance of silicone coating adhesives
As can be seen from the experimental data in Table 1, the functional additive prepared by the invention has lower effective viscosity, higher product yield and better compatibility with the hydroxyl silicone oil.
The experimental data in table 2 show that the functional additive prepared by the invention can effectively improve various performances of the organic silicon three-proofing coating adhesive when added into the organic silicon three-proofing coating adhesive, and the addition of the functional additive can effectively improve the adhesive force of the three-proofing coating adhesive (from level 2 to level 0) and obviously improve the oil resistance, solvent resistance, ozone resistance and smoke resistance of the three-proofing coating adhesive through comparison between the front and the back.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. The functional assistant for the liquid silicone rubber is characterized by being mainly formed by polymerizing an acrylate monomer, vinyl siloxane and other vinyl monomer compounds according to the mass ratio of 80-300: 100-.
2. The functional assistant for liquid silicone rubber according to claim 1, wherein the acrylate monomer is one or a combination of acrylic acid, methyl acrylate, butyl acrylate, hydroxyethyl methacrylate and perfluoroalkyl ethyl acrylate.
3. The functional aid for liquid silicone rubber according to claim 1, characterized in that the vinyl silicone is a vinyl silicone oil.
4. The functional assistant for liquid silicone rubber according to claim 1, wherein the other vinyl monomer compound is one or a combination of styrene, vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, acrylonitrile, and vinyl acetate.
5. The functional aid for liquid silicone rubber according to any one of claims 1 to 4, wherein the functional aid has a solubility parameter of 10 to 25, a degree of polymerization of 1 to 100, and a molecular weight of 1000-.
6. A method for preparing a functional aid for liquid silicone rubber according to any one of claims 1 to 5, comprising the steps of: mixing vinyl siloxane, acrylate monomers, a chain transfer agent and a solvent, then dropwise adding a chain initiator, other vinyl monomer compounds and the solvent, controlling the temperature to be 40-120 ℃, reacting for 2-8 hours to obtain a primary sample, then extracting, distilling under reduced pressure, removing the solvent, and finally obtaining light yellow viscous liquid, namely the functional assistant for the liquid silicone rubber.
7. The preparation method according to claim 6, wherein the solvent is selected from one or more of toluene, xylene, acetone, butanone, ethyl acetate, heptane and cyclohexane.
8. The preparation method of claim 6, wherein the chain initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, potassium persulfate and ammonium persulfate, and the addition amount of the chain initiator is 0.1-10% of the total mass of all raw materials.
9. The preparation method of claim 6, wherein the chain transfer agent is selected from one or more of isooctyl 3-mercaptopropionate, n-dodecyl mercaptan, quaternary cyclopentadienyl tetraethanol tetrakis (3-mercaptopropionate) and ethyl hexanol 3-mercaptopropionate, and the addition amount of the chain transfer agent is 0.01-10% of the total mass of all raw materials.
10. Use of a functional aid according to any one of claims 1 to 5 or prepared by the preparation process according to any one of claims 6 to 9, wherein the functional aid is used in admixture with a liquid silicone rubber.
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